Alkoxylation products and process for preparing them by means of DMC catalysts

Abstract

Novel alkoxylation products containing lateral hydroxyl groups or bearing lateral C—C double bonds and a process for preparing them by means of an alkoxylation reaction of halogenated alkylene oxides using double metal cyanide (DMC) catalysts and subsequent elimination of chlorine.

The invention claimed is: 
     
       1. A compound which includes:
 a structural element [—CH 2 —CH(CH 2 OH)—O—] and/or a structural element [—CH 2 —C(═CH 2 )—O—]; 
 wherein the compound has the formula (I):
   A-[O—(CH 2 —CHR—O—) n —(CH 2 —CH(CH 2 OH)—O—) m1 —(CH 2 —C(═CH 2 )—O—) m2 —(CH 2 —CH(CH 3 )—O—) o —H] a1   (I)
 
 where a1 is from 1 to 8; 
 where A is either hydrogen, or a radical, of an organic starter compound, having at least one carbon atom; 
 where the radicals R are each, independently of one another, either hydrogen, CH 2 —Cl, an alkyl group having 2-18 carbon atoms, or an aromatic radical; 
 where (a1×m1) is from 0 to 50; 
 where (a1×m2) is from 0 to 50; 
 where (a1×n) is from 0 to 200; 
 where (a1×o) is from 1 to 1000; 
 where the sum (a1×(m1+m2)) is from 2 to 50; and 
 where (a1×m1) is 2 or greater than 2 when (a1×m2) is zero. 
 
 
     
     
       2. A compound according to  claim 1 ;
 wherein the molar proportion of the units having the index m 2  is from 20 to 100% based on the sum of the units having the indices m 1  and m 2 , which adds up to 100%. 
 
     
     
       3. A compound according to  claim 2 ;
 wherein the molar proportion of the units having the index m 2  is from 30 to 90% based on the sum of the units having the indices m 1 , and m 2 , which adds up to 100%. 
 
     
     
       4. A compound according to  claim 1 ;
 wherein the compounds of the formula (I) have an oxypropylene group (index o) as last monomer unit. 
 
     
     
       5. A compound according to  claim 1 ;
 wherein the radical A is a radical of a monohydric or polyhydric polyether alcohol and/or a radical of a monohydric or polyhydric alcohol. 
 
     
     
       6. A compound according to  claim 1 ;
 wherein the compound has a weight average molar mass of from 200 to 50000 g/mol. 
 
     
     
       7. A process for preparing compounds comprising the structural element [—CH 2 —CH(CH 2 OH)—O—] and/or the structural element [—CH 2 —C(═CH 2 )—O—] using double metal cyanide catalysts, the process comprising:
 process step 1, which includes:
 reacting:
 (a) one or more compounds of the formula (II):
   A—OH  (II)
 
 
 where A=hydrogen or an organic radical having at least one carbon atom; 
 
 with:
 (b) epichlorohydrin and propylene oxide and optionally one or more further alkylene oxides having from 2 to 18 carbon atoms; 
 
 in the presence of:
 (c) a double metal cyanide catalyst ; 
 
 at a temperature of from 60 to 250° C. and a pressure of from 0.02 bar to 100 bar (absolute) to give an alkoxylation product having one or more chemically bound chlorine atoms; and 
 
 process step (2), which includes:
 reacting the chlorinated alkoxylation product obtained in process step 1), with one or more metal hydroxide or metal alkoxide compounds, at a temperature of 30-200° C. with complete or partial elimination of the organically bound chlorine; 
 wherein the reacting optionally takes place in the presence of water; 
 wherein the reacting optionally takes place in the presence of organic solvents; and 
 wherein the reacting optionally takes place in the presence of phase transfer catalysts; 
 
 wherein the process optionally further comprises process (3), which includes:
 work-up of the reaction product by at least one of:
 (a) neutralization by means of an inorganic or organic acid; 
 (b) distillation of water and/or solvent; 
 (c) removal of chloride salts by phase separation; and 
 (d) filtration. 
 
 
 
     
     
       8. The process according to  claim 7 ;
 wherein at least one of sodium hydroxide, potassium hydroxide, ethanolic or methanolic solutions of NaOH or KOH, and mixtures thereof, is used as metal hydroxide; and/or 
 wherein at least one of sodium methoxide, potassium methoxide, methanolic solutions, and mixtures thereof; is used as metal alkoxide. 
 
     
     
       9. The process according to  claim 8 ;
 wherein at least one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium methoxide solution, a potassium methoxide solution, and mixtures thereof, having a concentration of from 10 to 50% by weight is used. 
 
     
     
       10. The process according to  claim 7 ;
 wherein the hydroxide and/or alkoxide is used in an equimolar amount or a molar excess based on the bound chlorine in the alkoxylation product. 
 
     
     
       11. The process according to  claim 10 ;
 wherein from 1.0 mol to 3 mol of hydroxide or alkoxide is used per 1 mol of chlorine. 
 
     
     
       12. The process according to  claim 7 ;
 a compound according to  claim 1  is prepared. 
 
     
     
       13. The process according to  claim 7 ;
 wherein a composition is obtained which comprises a compound including:
 a structural element [—CH 2 —CH(CH 2 OH)—O] and/or a structural element [—CH 2 —C(═CH 2 )—O—]; 
 wherein the compound has the formula (I):
   A-[O—(CH 2 —CHR—O—) n —(CH 2 —CH(CH 2 OH)—O—) m1 —(CH 2 —C(═CH 2 )—O—) m2 —(CH 2 —CH(CH 3 )—O—) o —H] a1   (I)
 
 
 
 where a1 is from 1 to 8; 
 where A is either hydrogen or a radical of an organic starter compound, having at least one carbon atom; 
 where the radicals R are each, independently of one another, either hydrogen, CH 2 —Cl, an alkyl group having 2-18 carbon atoms, or an aromatic radical; 
 where (a1×m1) is from 0 to 50; 
 where (a1×m2) is from 0 to 50; 
 where (a1×n) is from 0 to 200; 
 where (a1×o) is from 1 to 1000; 
 where the sum (a1×(m1+m2)) is from 2 to 50; and 
 where (a1×m1) is 2 or greater than 2 when (a1×m2) is zero. 
 
     
     
       14. A composition which includes a compound according to  claim 1 .